CN103396119A - A kind of preparation method of single-phase pyrochlore type La2Zr2O7 nanopowder - Google Patents
A kind of preparation method of single-phase pyrochlore type La2Zr2O7 nanopowder Download PDFInfo
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- CN103396119A CN103396119A CN2013103727032A CN201310372703A CN103396119A CN 103396119 A CN103396119 A CN 103396119A CN 2013103727032 A CN2013103727032 A CN 2013103727032A CN 201310372703 A CN201310372703 A CN 201310372703A CN 103396119 A CN103396119 A CN 103396119A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000011858 nanopowder Substances 0.000 title claims abstract description 18
- 229910002230 La2Zr2O7 Inorganic materials 0.000 title abstract 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 48
- 230000032683 aging Effects 0.000 claims abstract description 12
- 239000002243 precursor Substances 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 9
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 9
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract 3
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract 3
- 239000000843 powder Substances 0.000 claims description 52
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 38
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- 238000003756 stirring Methods 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 7
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 239000011240 wet gel Substances 0.000 claims description 4
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims 4
- 239000000499 gel Substances 0.000 claims 2
- 229910002422 La(NO3)3·6H2O Inorganic materials 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 7
- 239000012720 thermal barrier coating Substances 0.000 abstract description 5
- 150000001408 amides Chemical class 0.000 abstract description 3
- 239000008139 complexing agent Substances 0.000 abstract description 3
- 238000005245 sintering Methods 0.000 abstract description 3
- 230000036571 hydration Effects 0.000 abstract description 2
- 238000006703 hydration reaction Methods 0.000 abstract description 2
- 239000001301 oxygen Substances 0.000 abstract description 2
- 239000013078 crystal Substances 0.000 abstract 1
- 239000002270 dispersing agent Substances 0.000 abstract 1
- 239000005416 organic matter Substances 0.000 abstract 1
- 239000011253 protective coating Substances 0.000 abstract 1
- -1 polyoxyethylene Polymers 0.000 description 25
- 239000012071 phase Substances 0.000 description 20
- 239000000243 solution Substances 0.000 description 19
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 17
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 17
- 239000007788 liquid Substances 0.000 description 17
- 239000011259 mixed solution Substances 0.000 description 15
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 8
- 230000008569 process Effects 0.000 description 6
- 238000003980 solgel method Methods 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000009413 insulation Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000000975 co-precipitation Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 238000007750 plasma spraying Methods 0.000 description 3
- UJQGVDNQDFTTLZ-VNHYZAJKSA-N Costic acid Natural products C1CCC(=C)[C@@H]2C[C@H](C(=C)C(O)=O)CC[C@]21C UJQGVDNQDFTTLZ-VNHYZAJKSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- QXRKIZKJLNNMNC-UHFFFAOYSA-N 11,13-Dihydrocostic acid Natural products CC(C1CCC2(C)CCCC(=C)C2C1)C(=O)O QXRKIZKJLNNMNC-UHFFFAOYSA-N 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- SGZOYHLQNUSAIL-UHFFFAOYSA-N Ioscostussaeure Natural products C1C(C(=C)C(O)=O)CCC2(C)CCCC(C)=C21 SGZOYHLQNUSAIL-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- UTXMCYDEIZPGME-UHFFFAOYSA-N beta-Isocostic acid Natural products C1CC(C(=C)C(O)=O)CC2C(C)=CCCC21C UTXMCYDEIZPGME-UHFFFAOYSA-N 0.000 description 1
- UJQGVDNQDFTTLZ-UHFFFAOYSA-N beta-costic acid Natural products C1CCC(=C)C2CC(C(=C)C(O)=O)CCC21C UJQGVDNQDFTTLZ-UHFFFAOYSA-N 0.000 description 1
- 239000013590 bulk material Substances 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical group [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
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- 230000000052 comparative effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910001960 metal nitrate Inorganic materials 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000011224 oxide ceramic Substances 0.000 description 1
- 229910052574 oxide ceramic Inorganic materials 0.000 description 1
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- 239000000126 substance Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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Abstract
The invention relates to a preparation method of single-phase pyrochlore-type La2Zr2O7 nano-powder. The preparation method is characterized in that the La2Zr2O7 nano-powder is obtained by ageing, drying and high-temperature roasting by using Zr<4+> and La<3+> hydration inorganic salt as a precursor, citric acid as a complexing agent, an amide organic matter as a gel accelerant and polyethylene glycol as a dispersing agent. The single-phase pyrochlore-type La2Zr2O7 nano-powder has the advantages that the particle size of the obtained La2Zr2O7 nano-powder is 20-100nm, the molar ratio of Zr to La is approximate to 1:1, the crystal structure of the La2Zr2O7 nano-powder is single-phase pyrochlore-type, and the La2Zr2O7 nano-powder has high degree of crystallinity and excellent performances such as low heat conduction, sintering resistance, good high-temperature stability and the like and is applied to the field of thermal barrier coatings of aviation turbine engines and protective coatings in high-temperature wet-oxygen environments.
Description
Technical field
The present invention relates to a kind of preparation method of single-phase RE oxide ceramics superfine powder, particularly relate to sol-gel method and prepare single-phase pyrochlore-type La
2Zr
2O
7Nano-powder.
Background technology
Along with fuel gas temperature and the pressure of aero-turbine improves constantly, traditional thermal structure alloy can't satisfy the demands, and improving stability and the service life of material under higher temperature is problem in the urgent need to address.At present, the surface temperature that thermal barrier coating (TBCs) technology is passed through to reduce bulk material, to improve the engine service life, has become the focus of current research.Usually the method that prepare TBCs has plasma spraying method, electro beam physics vapour deposition method, chemical Vapor deposition process and lf method etc., wherein, develop comparative maturity, most widely used be plasma spraying method, its raw material is powder body material.Zirconic acid lanthanum (La
2Zr
2O
7) be a kind of material of pyrochlore constitution, have lower thermal conductivity, below fusing point without the excellent properties such as phase transformation, Heat stability is good as in the preferred powder body material that uses under high temperature, and prepare that single crystalline phase, degree of crystallinity are high, good dispersity, La that granularity is little
2Zr
2O
7Powder is to affect plasma spray La
2Zr
2O
7The key of coating performance.
Preparation La commonly used
2Zr
2O
7The method of powder is solid phase method, but solid reaction process synthesis temperature higher (1550～1650 ℃) is difficult to controlling composition and crystallization phases, and the La that obtains of solid phase method
2Zr
2O
7Powder grain size is large, size distribution is inhomogeneous, and this has just limited its application at high temperature.Liquid preparation methods La
2Zr
2O
7Advantage be: precursor is mixed with molecular level, thereby the powder granule that finally obtains is less and be uniformly dispersed.More ripe liquid phase preparation technology is coprecipitation method at present, and patent CN101407336A discloses a kind of La
2Zr
2O
7The co-precipitation preparation method of powder, will contain Zr
4+And La
3+Two kinds of precursor solutions mix, add precipitation agent to generate precipitation, obtain La through washing, high-temperature roasting
2Zr
2O
7Powder, the powder granule degree that this method obtains is large, and contains the impurity phase fluorite structure in structure.
Sol-gel method belongs to the liquid phase method category, compares preparation La with traditional coprecipitation method
2Zr
2O
7Powder granule is less, can reach nanometer level, and phase consists of single pyrrhite phase, and uniform particles and purity are high, have the advantages such as anti-sintering, high-temperature-phase good stability, physical strength height, are more suitable for the powder body material as plasma spraying TBCs.Document 1 " Liu Shuxin, Haibin Wang. original position is synthesized La
2Zr
2O
7-YSZ matrix material and high-temperature thermal stability Journal of Sex Research, Chinese powder technology, 2011,17 (4): 65-70. " announced a kind of La
2Zr
2O
7The sol-gel process for preparing of-YSZ powder, it adopts metal nitrate as raw material, and citric acid has prepared La as complexing agent
2Zr
2O
7-YSZ powder, but owing to not adding dispersion agent, the particle size of gained powder is larger, reaches micron order.Document 2 " Vladimir Sevast ' yanov, Elizaveta Simonenko, Nikolai Simonenko, et al.Synthesis of finely dispersed La
2Zr
2O
7, La
2Hf
2O
7, Gd
2Zr
2O
7And Gd
2Hf
2O
7Oxides.Mendeleev Commun., 2013,23:17-18. " adopt metal inorganic salt as raw material, add concentrated nitric acid, citric acid, ethylene glycol, adopt ammoniacal liquor to regulate the pH value, prepare La
2Zr
2O
7Nano-powder, still can't slowly control the variation of pH value due to ammoniacal liquor, colloidal solid is difficult to evenly grow up, thereby causes crystallinity poor.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, solve existing sol-gel method and prepare La
2Zr
2O
7The problem such as powder high-temperature stability deficiency, easy-sintering, physical strength are not high, provide that a kind of single crystalline phase, degree of crystallinity are high, good dispersity, La that granularity is little
2Zr
2O
7Powder preparation method.
The present invention is achieved through the following technical solutions:
1, preparation precursor solution:
Adopt metal hydration inorganic salt as precursor, adopt the mixed solution of water and alcohol as solvent, will contain Zr
4+And La
3+Hydrated inorganic salt slowly join respectively in the mixed solution of water and alcohol, continue stirring and dissolving, obtain two kinds of precursor solutions, each component molar content ratio is respectively: Zr
4+: H
2O: alcohol=1:5～8:10, La
3+: H
2O: alcohol=1:0.5～2:10;
Wherein, contain Zr
4+Hydrated inorganic salt be ZrOCl
28H
2O or Zr (NO
3)
45H
2O, contain La
3+Hydrated inorganic salt be La (NO
3)
36H
2O or LaCl
36H
2O, alcoholic solvent are methyl alcohol, ethanol or propyl alcohol, preferred alcohol;
2, prepare colloidal sol:
Two kinds of solution of step 1 gained are pressed component mol ratio Zr
4+: La
3+=1:1 mixes and continues stirring, adds successively citric acid, and mol ratio is citric acid: Zr
4+=0.1～0.4:1; Add polyoxyethylene glycol constituent mass ratio to be: polyoxyethylene glycol: Zr
4+=1:1～7.5, wherein, the number-average molecular weight of polyoxyethylene glycol can be 600～20000; Add methane amide or N-METHYLFORMAMIDE, mol ratio is: methane amide or N-METHYLFORMAMIDE: Zr
4+=0.1～2:1, continue to stir 1～5h with above-mentioned mixed solution, forms colloidal sol;
3, aging:
Colloidal sol is incubated aging under 60～90 ℃, continues 10～24h, obtain wet gel; Selection process is the aging 15h of insulation under 80 ℃ of conditions, and aging temperature is higher, and digestion time shortens relatively;
4, drying:
100～200 ℃ of dryings, be 5～10h time of drying, obtains xerogel with wet gel; Selection process is dry 6h under 120 ℃ of conditions, and drying temperature is higher, and relatively shorten time of drying;
5, high-temperature roasting:
Xerogel is incubated 1～5h again after the temperature rise rate of 1～10 ℃/min rises to 1000～1200 ℃,, with the stove cooling, obtains La
2Zr
2O
7Powder, selection process are that 5 ℃/min rises to 1200 ℃, and insulation 2h, lower the temperature with stove.
The present invention is a kind of improved sol-gel process for preparing, with traditional sol-gel method, compares, and precursor used reduces greatly than traditional metal alkoxide cost, and citric acid strengthens the colloid network as complexing agent; Adopt polyoxyethylene glycol as dispersion agent, polyoxyethylene glycol has the characteristic of tensio-active agent, can make the colloidal solid of containing metal-oxygen key even at solvent dispersion, reduces the size of gelation gained micelle, finally reduces the granular size of gained powder; Adopt amides additive control gelation process, the amides additive is through being hydrolyzed the H that can remove in solution
+, improve the pH value of solution, the effect that this process is regulated pH value than strong alkaline substances such as ammoniacal liquor slowly many, thereby can guarantee colloidal solid slowly, the even growth, the network structure that full cross-linked formation is good, obtain the good La of crystallinity after high-temperature roasting
2Zr
2O
7Powder.The method technique is simple, cost is low, corrosion-free to equipment, prepared powder is that single pyrrhite phase, elementary composition near stoichiometric proportion, good crystallinity, granular size are nano level, are uniformly dispersed.
Raw material required for the present invention all can obtain by open channel from market, and testing installation is common equipment.
Description of drawings
Fig. 1 is the La of the embodiment of the present invention 1 preparation
2Zr
2O
7The SEM photo of powder;
Fig. 2 is the La of the embodiment of the present invention 1 preparation
2Zr
2O
7The TEM photo of powder;
Fig. 3 is the La of the embodiment of the present invention 1 preparation
2Zr
2O
7The XRD spectra of powder;
Fig. 4 is the La of the embodiment of the present invention 3 preparations
2Zr
2O
7The SEM photo of powder;
Fig. 5 is the La of the embodiment of the present invention 3 preparations
2Zr
2O
7The TEM photo of powder;
Fig. 6 is the La of the embodiment of the present invention 3 preparations
2Zr
2O
7The XRD spectra of powder;
Embodiment
The invention will be further described by the following examples, but protection domain is not subjected to the restriction of these embodiment.Should be understood that in addition after having read content of the present invention, those skilled in the art can make various changes or modifications the present invention, these equivalent form of values fall within appended claims limited range of the present invention equally.
Embodiment 1
A kind of single-phase pyrochlore-type La of the present invention's preparation
2Zr
2O
7Nano-powder mainly contains following steps:
(1) ZrOCl in molar ratio
28H
2O:H
2O:CH
3OH=1:5:10, with 5.00g ZrOCl
28H
2O slowly joins in the mixed solution of 1.40g water and 4.97g methyl alcohol, constantly stirs, and obtains clear solution A liquid; Simultaneously, La (NO in molar ratio
3)
36H
2O:H
2O:CH
3OH=1:0.5:10, with 6.66g La (NO
3)
36H
2O slowly adds in the mixed solution of 0.14g water and 4.97g methyl alcohol, constantly stirs, and obtains clear solution B liquid;
(2) A liquid and B liquid are mixed, obtain transparent mixing solutions, stir;
(3) under the condition that continue to stir, successively in mixed solution in molar ratio: citric acid: Zr
4+=0.1:1 adds citric acid 0.33g, polyoxyethylene glycol in mass ratio: Zr
4+=1:1 adds polyoxyethylene glycol 1.41g, and wherein, the number-average molecular weight of polyoxyethylene glycol is 600, in molar ratio N-METHYLFORMAMIDE: Zr
4+=0.1:1 adds N-METHYLFORMAMIDE 0.09g, stirs 1h, obtains colloidal sol;
(4) with colloidal sol at 60 ℃ of aging 24h, then through 100 ℃ of dry 10h, obtain faint yellow xerogel;
(5) xerogel is risen to 1000 ℃ through 1 ℃/min in retort furnace, then be incubated 5h,, with the stove cooling, obtain La
2Zr
2O
7Powder.
The present embodiment gained La
2Zr
2O
7As shown in Figure 1, visible gained powder is uniformly dispersed the SEM photo of powder; The present embodiment gained La
2Zr
2O
7As shown in Figure 2, the particle size of visible powder is nano level, approximately 40～100nm to the TEM photo of powder; The present embodiment gained La
2Zr
2O
7As shown in Figure 3, the phase composite of visible powder is single for the XRD spectra of powder, and structure is pyrochlore-type, and crystallinity is good.
A kind of single-phase pyrochlore-type La of the present invention's preparation
2Zr
2O
7Nano-powder mainly contains following steps:
(1) ZrOCl in molar ratio
28H
2O:H
2O:C
3H
7OH=1:8:10, with 5.00g ZrOCl
28H
2O slowly joins in the mixed solution of 2.24g water and 9.31g propyl alcohol, constantly stirs, and obtains clear solution A liquid; Simultaneously, La (NO in molar ratio
3)
36H
2O:H
2O:C
3H
7OH=1:2:10, with 6.66g La (NO
3)
36H
2O slowly adds in the mixed solution of 0.56g water and 9.31g propyl alcohol, constantly stirs, and obtains clear solution B liquid;
(2) A liquid and B liquid are mixed, obtain transparent mixing solutions, stir;
(3) under the condition that continue to stir, successively in mixed solution in molar ratio: citric acid: Zr
4+=0.4:1 adds citric acid 1.32g, polyoxyethylene glycol in mass ratio: Zr
4+=1:7.5 adds polyoxyethylene glycol 0.19g, and wherein, the number-average molecular weight of polyoxyethylene glycol is 20000, in molar ratio methane amide: Zr
4+=2:1 adds methane amide 1.40g, stirs 5h, obtains colloidal sol.
(4) with colloidal sol at 90 ℃ of aging 10h, then through 200 ℃ of dry 5h, obtain brown xerogel.
(5) xerogel is risen to 1200 ℃ through 10 ℃/min in retort furnace, then be incubated 1h,, with the stove cooling, obtain La
2Zr
2O
7Powder.
The present embodiment gained La
2Zr
2O
7Powder, particle size is nano level, is about 40～80nm, powder consist of single pyrrhite phase La
2Zr
2O
7
Embodiment 3
A kind of single-phase pyrochlore-type La of the present invention's preparation
2Zr
2O
7Nano-powder mainly contains following steps:
(1) ZrOCl in molar ratio
28H
2O:H
2O:C
2H
5OH=1:6:10, with 5.00g ZrOCl
28H
2O slowly joins in the mixed solution of 1.68g water and 7.14g ethanol, constantly stirs, and obtains clear solution A liquid; Simultaneously, La (NO in molar ratio
3)
36H
2O:H
2O:C
2H
5OH=1:1:10, with 6.66g La (NO
3)
36H
2O slowly adds in the mixed solution of 0.28g water and 7.14g ethanol, constantly stirs, and obtains clear solution B liquid;
(2) A liquid and B liquid are mixed, obtain transparent mixing solutions, stir;
(3) under the condition that continue to stir, successively in mixed solution in molar ratio: citric acid: Zr
4+=0.2:1 adds citric acid 0.65g, polyoxyethylene glycol in mass ratio: Zr
4+=1:5 adds polyoxyethylene glycol 0.28g, and wherein, the number-average molecular weight of polyoxyethylene glycol is 20000, in molar ratio methane amide: Zr
4+=1:1 adds methane amide 0.70g, stirs 3h, obtains colloidal sol;
(4) with colloidal sol at 80 ℃ of aging 15h, then through 120 ℃ of dry 6h, obtain faint yellow xerogel;
(5) xerogel is risen to 1200 ℃ through 5 ℃/min in retort furnace, insulation 2h,, with the stove cooling, obtain La
2Zr
2O
7Powder.
The present embodiment gained La
2Zr
2O
7As shown in Figure 4, visible gained powder is uniformly dispersed the SEM photo of powder; The present embodiment gained La
2Zr
2O
7As shown in Figure 5, the particle size of visible powder is nano level, approximately 20～80nm to the TEM photo of powder; The present embodiment gained La
2Zr
2O
7As shown in Figure 6, the phase composite of visible powder is single for the XRD spectra of powder, and structure is pyrochlore-type, and crystallinity is good.
Embodiment 4
A kind of single-phase pyrochlore-type La of the present invention's preparation
2Zr
2O
7Nano-powder mainly contains following steps:
(1) Zr (NO in molar ratio
3)
45H
2O:H
2O:C
2H
5OH=1:8:10, with 5.00g Zr (NO
3)
45H
2O slowly joins in the mixed solution of 1.66g water and 5.31g ethanol, constantly stirs, and obtains clear solution A liquid; Simultaneously, LaCl in molar ratio
36H
2O:H
2O:C
2H
5OH=1:1:10, with 2.86g LaCl
36H
2O slowly adds in the mixed solution of 0.21g water and 5.31g ethanol, constantly stirs, and obtains clear solution B liquid;
(2), with mixing such as A liquid and B liquid, obtain transparent mixing solutions, stir;
(3) under the condition that continue to stir, successively in mixed solution in molar ratio: citric acid: Zr
4+=0.1:1 adds citric acid 0.24g, polyoxyethylene glycol in mass ratio: Zr
4+=1:7.5 adds polyoxyethylene glycol 0.14g, and wherein, the number-average molecular weight of polyoxyethylene glycol is 20000, in molar ratio methane amide: Zr
4+=1:1 adds methane amide 0.52g, stirs 5h, obtains colloidal sol;
(4) with colloidal sol at 80 ℃ of aging 20h, then through 120 ℃ of dry 5h, obtain faint yellow xerogel;
(5) xerogel is risen to 1200 ℃ through 5 ℃/min in retort furnace, insulation 2h,, with the stove cooling, obtain La
2Zr
2O
7Powder.
The present embodiment gained La
2Zr
2O
7Powder, particle size is nano level, is about 20～90nm, powder consist of single pyrrhite phase La
2Zr
2O
7
Claims (7)
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|---|---|---|---|
| CN201310372703.2A CN103396119B (en) | 2013-08-25 | 2013-08-25 | A kind of preparation method of single-phase pyrochlore type La2Zr2O7 nanopowder |
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| CN103896620A (en) * | 2014-03-11 | 2014-07-02 | 中国人民解放军国防科学技术大学 | Hierarchical porous La2Zr2O7 ceramics and its preparation method |
| CN104355614A (en) * | 2014-10-23 | 2015-02-18 | 浙江大学 | Preparation method of porous aluminum titanate block |
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| CN105923650A (en) * | 2016-04-20 | 2016-09-07 | 陕西科技大学 | A method for preparing nano-Bi2Zr2O7 powder by precipitation and calcination |
| CN107267148A (en) * | 2017-07-26 | 2017-10-20 | 齐齐哈尔大学 | A kind of terbium ion doping zirconic acid lanthanum fluorescent material and preparation method thereof |
| CN108439462A (en) * | 2018-03-28 | 2018-08-24 | 江苏师范大学 | A kind of preparation method of pyrochlore-type rare earth titanate powder |
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| CN109868058A (en) * | 2019-01-11 | 2019-06-11 | 上海交通大学 | Asymmetric hollow zirconic acid lanthanum microballoon enhancing silicon rubber insulating moulding coating and its application |
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| CN110372036A (en) * | 2019-08-23 | 2019-10-25 | 中国人民解放军国防科技大学 | A kind of ternary transition metal oxide powder and its preparation method |
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| CN112960979A (en) * | 2021-02-25 | 2021-06-15 | 中国科学院新疆理化技术研究所 | Zirconate system high-temperature negative temperature coefficient thermistor material and preparation method thereof |
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| CN103803973A (en) * | 2013-12-26 | 2014-05-21 | 浙江大学 | Compact pure-phase lanthanum zirconate ceramic with low thermal conductivity and high strength, and preparation method thereof |
| CN103803973B (en) * | 2013-12-26 | 2015-09-09 | 浙江大学 | Low thermal conductivity, high strength dense pure phase lanthanum zirconate ceramics and preparation method thereof |
| CN103896620A (en) * | 2014-03-11 | 2014-07-02 | 中国人民解放军国防科学技术大学 | Hierarchical porous La2Zr2O7 ceramics and its preparation method |
| CN103896620B (en) * | 2014-03-11 | 2015-08-12 | 中国人民解放军国防科学技术大学 | Classifying porous La 2zr 2o 7pottery and preparation method thereof |
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| CN105923650A (en) * | 2016-04-20 | 2016-09-07 | 陕西科技大学 | A method for preparing nano-Bi2Zr2O7 powder by precipitation and calcination |
| CN107267148A (en) * | 2017-07-26 | 2017-10-20 | 齐齐哈尔大学 | A kind of terbium ion doping zirconic acid lanthanum fluorescent material and preparation method thereof |
| CN108439462A (en) * | 2018-03-28 | 2018-08-24 | 江苏师范大学 | A kind of preparation method of pyrochlore-type rare earth titanate powder |
| CN108439462B (en) * | 2018-03-28 | 2020-09-22 | 新沂市东方硕华光学材料有限公司 | Preparation method of pyrochlore type rare earth titanate powder |
| CN109081692A (en) * | 2018-09-05 | 2018-12-25 | 东台市圣德尔耐热材料有限公司 | A kind of Yb3+/Ce4+Codope La2Zr2O7High-temperature flame-proof thermal insulation ceramics material and preparation method |
| CN109868058A (en) * | 2019-01-11 | 2019-06-11 | 上海交通大学 | Asymmetric hollow zirconic acid lanthanum microballoon enhancing silicon rubber insulating moulding coating and its application |
| CN110102248A (en) * | 2019-06-21 | 2019-08-09 | 清华大学 | A kind of surface oxygen defect porous metal oxide material and its preparation and application |
| CN110372036A (en) * | 2019-08-23 | 2019-10-25 | 中国人民解放军国防科技大学 | A kind of ternary transition metal oxide powder and its preparation method |
| CN111204800A (en) * | 2020-02-27 | 2020-05-29 | 东南大学 | A kind of preparation method of lanthanum zirconate nanoparticles |
| CN112960979A (en) * | 2021-02-25 | 2021-06-15 | 中国科学院新疆理化技术研究所 | Zirconate system high-temperature negative temperature coefficient thermistor material and preparation method thereof |
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